Method of treating complex liquid partial oxidation products and articles produced thereby



Faiented Jan. 17, was

7. s'rrss unis E'GSEEH Y JAMES, F EITTS BURGH. PENNSYLVANId, ASSIGNQR T0 CLARENCE I EQ BYBNES, OF SEWICKLEY, PENNSYLVANIA, TRUSTEE EETIHOD GE TREATING? COMPLEX LIQUID TARTIAL OXIDATION PRODUCTS AND ARTICLES PRODUCED THEREBY Ne Drawing. Application .filed July 13, 1920, Serial No. 520,715. Renewed December 7, 1923, a

In several of my copending applications such as Serial No. 272,567, filed January 22, 191$),f0r process of making aldehyde fatty acids, and Serial No. 281,124, filed March 7, 1919, now Patent No. 1,697,653, patented J an. i, 1929,- for intermediate partial oxidation product and method of making the same, I havedescrihed methods for the manufacture of intermediate oxidation products from mineral oils, including petroleum, shale oil, and a low temperature distillate of coal, by a method of partial combustion. The prodnets of such a. process lie in the range from. alcohols to aldehyde fatty acids and are mainly alcohols, aldehyde-alcohols, aldehydes, anhydrides, inner esters or lactone bodies, aldehyde fatty acids and similar compounds.

These products are present in different mo-- lecular weights, making the liquid mixture diificult to treat for obtainin difi'erent industrialproducts. I have discovered that fractioningsucha liquid into fractions of diderentboiling ranges aids in obtaining products; although not separating one body or class of bodies, from another body or class of bodies. I have also found that these aldehyde fatty acids and someof the aldehydelike bodies may be resinified and converted into resin-like bodies of commercial use either by themselvesor in compounds; The resinifying of these acids may be carried out in diflferent ways; but L prefer to prepare soaps from the aldehyde fatty acids and then liberate and resinify the aldehyde fatty acids,

for examplefby treating the soaps with cold dilute solutions of hydrochloric acid. The

resin acids formed have ahigher melting pointthan the untreated aldehyde acids and have different chemical and physical properties. Where hydrochloric acid is used dif- 'ferent strengths of solution maybe employed, and the mixture is preferably allowed to stand at a slightly elevated temperature of say to 60 degrees until the excess hydrochloric acid solution has evaporated. The acidtreatment will give especially hard resins. It is also possible to effect resinification by maintaining the free aldehyde acids for a considerable time at a somewhat elevated temperature such as 95 to 100 C.

I will now describe some specific examples of resinifying these acids:

Ewample 1 The aldehyde fatty acids were prepared by'my partial combustion process from Pennsylvania gas oil, the product containing other compounds such as alcohols and aldehydes, together with some unconverted hydrocarbons. Potash soaps were then formed from the aldehyde fatty acids, these soaps being separated from the reaction mixture. The potash soaps were then treated cold with a 4% solution of hydrochloric acid to slight excess. .Under these conditions resinification took place almost immediately. The resinified acids were washed with water and dried. The color of the resin acid mixture was light brown; it was brittle'at room temperature; softened at 72 (1.; had an incipient melting point at100 C., and was completely melted at 120 C. i

I, This mixture of resin acids dissolved readily in benzol. The solvent evaporated rapidly, leaving .adark brown varnish coating which was hard and tough and possessed fine gloss.

Likewise, the varnish-paint applicability of the material was shown by incorporating various pigments with the resin acids in the In the various tests under this example the ticular mineral acid used was shown. The

soap was prepared by potash saponification on the reaction mixture resulting from partial combustion of a Wyoming petroleum fraction of .83 specific gravity.

(a) The separated soap was treated with effect of different concentrations of the par- 4% hydrochloric acid solution cold with agi-f .tation., The resin acid product was dark brown, fairly brittle at room temperature and softened at 65 C. It was semi-liquid at 9 i G. and completel melted at 104C.

(b) A portion 0 the same product was treated by liberating the aldehyde fatty acid benzol solution. With the evaporation of with a solvent.

(0) Another portion of the same product was treated by liberating the aldehyde fatty acids in treating with a 40% solution of hydrochloric acid in the cold. The resin acids produced were dark brown and too soft to crush.

Example 3 The product mixture was made from partial combustion oxidation of a fraction from Wyoming petroleum having a specific gra'vity of .85. In this experiment, the product containing the aldehyde fatty acids was distilled before saponification, the residue above 200 C. being taken for resinifying. Soap was formed and the acids liberated from the soap by treatment in the cold with 10% hydrochloric acid solution and the organic acids allowed to stand for four hours at a tempera ture of 90 C. in contact with an excess of the mineral acid. Finally the acid solution was evaporated at a temperature of 60? 6., about 24 hours being required for this step. The resin acid product was dark brown, brittle at room temperature and softened at 'C. It w was semi-liquid at ,C. and completely liquid at 96 C. When-dissolved in benzol and applied as a varnish it gave a fine glossy coat on hard wood. When mixed with pigments, it gave good paint films on wood and iron.

In the above experiments, where the resin acid products were incorporated with pigments and applied as a paint (usually with benzol solution), the film while hard after a few minutes from evaporation from the solvent, increases in hardness for several days. This is probably due partly to saponification through the "formation of hard insoluble soaps by interaction of the metallic oxides and resin acids, and partly to an oxidizing action of the pigment or an oxidation by the oxygen of the air, the pigment acting as a catalyst. Other acids may be used for liberating the resinified acids, such as, other halo-. gen acids, sulphuricacid and the acids of phosphorus, with modifications of the process as to temperature and concentration.

The aldehyde acids may be resinified by heat alone, or by a combination of heat and acid treatment. In addition to the pigments above noted, which are the ordinary oxides and other compounds known in this art, I may incorporate with the aldehyde resin acids, calcium, zinc, lead, or other soaps of the aldehyde acids or of the resinified acids. These additions are particularly valuable in neeaeea all films where moisture excluding properties are desired. These paint or varnish mixtures the basis of which is the resin acid products dissolved in a solvent such as benzol,

are specially valuable for water-proofing concrete. I In this case, the free acids react with the bases present in the concrete to form water-proof acid compounds on and in the cement or concrete.

'- Linseed oil may be used as solvent with or ment-s, etc. Also the fractioning of the liquid partial oxidation product presents several advantages in producing industrial products from one or more of the separated fractions.

Some of the claims herein relate to fractioning, and other claims toan d including fractioning are contained in other of m pending applications. I

Changes may be made in the method of resinifying the aldehyde fatty acids as well as in the manner of liberating the acids and treating them, without departing from my invention. 1

I claim:

1. As a new article of manufacture, a resinified portion of the product of partial oxidation containing aldehyde bodies of difierent' molecular weights. 1 p

2. As a new article of manufacture, a mixture containing a 'resinified'portion of the product of partial oxidation containing aldehyde bodies of different molecular weights.

3. As a new article of manufacture, a mixture containing resinified aldehyde fatty acid and an aldehyde fatty acid soap.

4. As anew article of manufacture, a composition containing resinified aldehyde fatty acigs and insoluble soaps of aldehyde fattyac1 s.

5. In the manufacture of synthetic resins, the steps consisting in separating aldehyde fatty acids from a partial combustion product containing said acids, together with other intermediate partial oxidation products, and resinifying said acids. 1 1

6. In the manufacture of synthetic resins, the steps consisting in separating aldehyde fatty acids from a partial combustion product containing said acids together with other intermediate partial oxidation products, resinifying said acids and then liberating the resinified acids.

7. In the manufacture-of synthetic resins,

lid

ganic acids of difierentmolecular weights of resinifiable types.

8. In the manufacture of synthetic resins,

the steps consisting of separatin a partial combustion product containing al ehyde fatty acids and other products into different portions of difi'erent molecular wei hts and resinifying'the aldehyde fatty aci s of the heavier portions. I 9. In the manufacture of synthetic resins the steps consisting of fractionating a liquid partial combustion product mixture containing aldehyde fatty acids into heavier and lighter portions and separating the aldehyde fatty acid from the heavier portion.

10. The method of treating a partial oxidation product containing aliphatic aldehyde-like bodies and oxygenated organic acids of difierent molecular weights, consistof difi'erent average molecular weights and I ing of fractionating the same into fractions subjecting a resulting fraction to further treatment.

11. The method of treating a partial oxidation product containing aliphatic aldehyde-like bodies and oxygenated organic acids-of different molecular weights, consisting of fractionating the same into fractions of different average molecular weights and resinifying a resulting fraction.

12. The method of treating a partial oxidation product containing aliphatic aldehyde-like bodies and oxygenated organic acids of diflerent molecular weights, con-j sistingof fractionating the same into fractions of difierent average molecular weights and separating the acids from a resulting fraction.

13. The method of treating a partial oxidation product containing aliphatic aldehyde-like bodies and oxygenated 1 organic acids of different molecular weights, consisting of fractionating the same into fractions of diiferent average molecular weights, separating the acids from a resulting fraction and resinifying said acids.

14:. In the treatmentof partial oxidation products of hydrocarbon oils, the ste s consisting of distilling a partial com ustion mixture containing aldehyde fatty acids u to about 200 C. andseparating the aci s from the remaining heavier portion of the mixture.

15. 'In the treatment of partial oxidation products ofhydrocarbon oils, the steps consisting of distilling a liquid partial combustion-mixture containing aldeh de fatty acids into a plurality of portions 0 different boiling ppint ranges, saponifying the acids in the heavier portions and liberating the said acids. 16. In the treatment of artial oxidation products of hydrocarbon 0115, the steps consisting of separating the liquid partial combustion mixture containing aldehyde fatty acids into portions of difi'erent boiling point ranges and saponifying the acids of the heavier range.

1.7. In the manufacture of synthetic resins, the steps consisting of separating the liquid partial combustion mixture containing aldehyde fatty acids into portions of different boiling point ranges, saponifying the acids of the heavier range and resinifyii rg,

18. llnthe treatment of liquid partial oxidation products of hydrocarbons containing a mixture in the range from alcohol to aldehyde fatty acids, the step consisting of resinifyin a fraction of said liquid mixture.

19, In the treatment of liquid partial oxidation products of hydrocarbons containing a mixture'in the range from alcohol to aldehyde fatty acids, the steps consisting of resinifying a fraction of said liquid mixture and separating the resinified matter from the remainder.

20. The method of treating a liquid partial-oxidation product containing oxygenated hydrocarbons in the range from alcohols to aldehyde fatty acids, consisting of fractionating such product to obtain fractions containing aldehyde bodies and then resinifying some of the aldehyde bodies in a resulting fraction. v

21. As a new article of manufacture, a resinified liquid partial-oxidation product containing resinifiable aliphatic aldehydelike bodies of different molecular weights.

22. As. a new article of manufacture, a resinified liquid partial oxidation product containing oxygenated organic acids of different molecular weights.

23. In-the treatment of a partial oxidation product having hydrocarbons which already contain artificially-introduced chemicallycombined oxygen to different degrees of oxidation, and 'which contain like bodies of different molecular Weights, the step consisting of fractionating the same into liquid fractions of different average molecular weights. 24. In the treatment of a partial oxidation product having hydrocarbons which already contain artificially-introduced chemicallycombined oxygen to different degrees of oxidation, including alcohols of difierent molecular weights and aldehyde-like bodies of dif ferent molecular weights, the ste consisting of fractionating the same into iquid fractions of difl'erent average molecular weights.

.25. In the treatment of a liquid partial oxidation product in the ran e from alcohols to organic acids and containing hydrocarbon.

tion to form a chemical compound of a portion of it, and separating said compound.

. 26. In the treatment of a liquid partial oxidation product in the range from alcohols to organic acids and containing hydrocarbon derivatives other than acids, the steps consisting of separating from the same a fraction by distillation containing a material percentage of aliphatic derivatives other than acids, and then saponifying a portion of said fraction and separating the saponified from the unsaponified portion of said fraction.

27. In the treatment of a liquid partial m oxidation product in the range from alcohols to organic acids and containing hydrocarbon derivatives other than acids, the steps consisting of separating from the same a fraction by distillation containing a material percentage of aliphatic derivatives other than acids, then saponifying a portion of said fraction and separating the saponified from the unsaponified portion of said fraction, and releasing the acids from the saponified portion. 2 28. In the'treatment of a liquid partial. oxidation product in the range from alcohols to organic acids and containing hydrocarbon derivatives other than acids, the steps consisting of separating from the same a fraction by distillation containing a material percentage of aliphatic derivatives other than acids, and then converting a portion of said fraction into resin acids by means of an alkali.

w 29. In. the treatment of a liquid partial oxidation product in the range from alcohols to organic acids and containing hydroj carbonderivatives other than acids, the steps consisting of separating from the same a traction by distillation containing a material percentage of aliphatic derivatives other than acids, and then forming resinified aldehyde acids from a portion of said fraction by means of an alkali.

30. In the treatment of a liquid partial oxidation product in the range from alcohols to organic acids and containing hydrocarbon derivatives other than acids, the steps consisting of separating from the same a frac- 435 tion by distillation containing a material percentage of aliphatic derivatives other than acids, and then converting a portion of said 1frtiction into resin acids by means of an al- 31. In the treatment of a partial oxidation product having hydrocarbons which already contain artificially-introduced chemicallycombined oxygen to different degrees of oxidation,v and which contain like bodies of different molecular Weights, the steps consisting of fractionating the same into liquid, fractions of different average molecular Weights and then treating a fraction With an alkali.

In testimony whereof, I have hereunto set (530 my hand.

JOSEPH HIDY JAMES. 

